Process of preparing a metallic phenolate salt of a hydroxyarylalkylamine product



. Patented .lamzl, .1947

- ;2,414,729 rnocnss or PREPARING A METALLIC PHENOLATE SALT OF A. HYDROXYARYL? ALKYLAMINEPRQDUCT Charles L. Fleming, In, Roselle Park, and John G.

McNab, Cranford, N. J., assignors-to Standard OilDevelopment Company, a corporation of Delaware No Drawing.- Application August 28,;1943, SerlalNo.500,372

3 Claims- (Cl. 260-53) This invention relates to the preparationoi 3 novel salts of amino compounds derived from substituted phenols by the introduction of an amino group into a side chain of such phenols,

causing. autocondensation of the product .and

neutralizing the compositionthus formed with a base.

This application is a continuation-in-part of our copending application Serial Number 425,132

filed December 31 .1941. a

The compositions herein described are partic- 'ularly useful as additives for mineral lubricating oils used in internal combustion engines, in which they act as inhibitors of oxidation and deposition of varnish on hot metal surfaces and as agents for promoting] engine cleanliness generally. They are also useful in lubricating compositions of high film strength for bearing and engine lution products'to condensation treatment after they have been prepared. The increase in the oil a solubility of the final products isdesirable in that it makes possible the preparation of li uid concentrates containing relatively large proportions, such as 25% or more, ofthe improving agents of this invention dissolved in hydrocarbon 011, these concentrated solutions being conveniently used for blending purposes. It may be noted' that the oil solubility offthe products also increases with the length of the alkyl substituent in the arcmatic nucleus.

The class of compounds which may be advantageously condensed and then reacted with a; base in accordance with the present invention may be defined broadly by the formula 'RAr(OH) -(R'--'N )a ii i hypoid gears, in which the salts act as inhibitors in which A.r is an aromatic nucleus, R is hydro! gen or an organicradical, especially an alkyl. aryl or aralkyl radical which may inturn conbrication and in the preparation or improved extreme pressure lubricants for use especially for of undesirable corrosion which is normally caused by the presence of materials containing chlorine,

1 which are used alone or in combination with other materials efiective in increasing the ex- 'treme pressure properties of the compounds, such as sulfur or phosphorus compounds.

The new salt compositions of the presentinvention may be regarded as salts of hydroxyarylj alkyl amines which have been caused to undergo autocondensation whereby the products become .oil soluble and exhibit more potent oxidation properties than the uncondensed compounds. Typical compounds are obtained by condensing an allryl phenol with an aldehyde, e. g., formaldehyde, in the presence of hydrogen chloride,

then reacting the resulting phenolic condensation product with ammonia or with an organic nitrogen base, heating the amino compound thus formed to liberate a portion of the nitrogen content of the same, and finally reacting the condensed amino compound with a suitable metallic base such as barium hydroxide. The solubility l of the amino compounds in hydrocarbon oils, as

well as the solubility of the salts obtained from them, varies with the degree of condensation or resinification, and their solubility and effectiveness arereadily increased by subjecting them to autocondensation conditions during their prepav ration, or by subjecting the simple amino reactain substituent groups, R is an alkyl linkage such as in which R represents either hydrogen or an alkyl or aryl group and may represent similar or different groups in the same molecule, and n is a small whole number. The compounds most preferred as lubricating oil additives are also characterized byhaving at least 4 carbon atoms in the alkyl group joined to the aryl nucleus and/or 5 to the nitrogen atom. The various substituent radicalsmay be attached at any position in the aryl nucleus and may be ortho, meta and/or para to the hydroxylgroup and to each other. Especially useful are the resinous condensation prod- 40 nets of. materials having the characteristic structure in which R is an alkyl group of at least 4 and preferably 5 to20 or more carbon atoms.

The autocondensation of the hydroxyaryl an amino compounds described above may be acusing higher temperatures.

that when the amines are formed by first reacting a phenol with an aldehyde in the presence of hydrogen chloride, and then treating the reaction product with ammonia, the time required for heating the final product varies with the chlorine content of the intermediate and increases with increase in chlorine content. Prod-- ucts formed. from intermediates containing from to preferably 12 to 14%, of chlorine are much desired, as the condensed nitrogeneousproducts formed from them are very effective lubricating oil improving agents. The condensation of theamines may be brought about not only by heating, but by standing at room temperature for a long period of time. Heating greatly hastens the autocondensation process, however. The

, heating may be carried out at atmospheric pressure or at higher pressures.

It is often convenient to seal the compound in a bomb and conduct the heating underthe pressure developed at 110? to 120 C. Whether the condensation is caused by heating or long standing, a characteristic change in the product is the elimination of sub- .stantial amounts of nitrogen, the quantities eliminated ranging from 10 to 75% of the original nitrogen content, depending upon conditions.

As stated above, the hydroxyarylalkylamines used to form the desired resinous products of the present invention may be readily prepared by reacting a phenol with an aldehyde in the presence of hydrogen chloride to form a hydroxybenzyl' chloride or like product and then reacting this product with ammonia or with an amine. The

layer separated from a lower fuming hydrochloric acid layer and was separately withdrawn from the reaction vessel. A portion of the upper layer,

after washing and removal of the benzene, yielded a viscous light red oil, crystallizing partly on standing. Analysis of a small sample of this oil indicated it to contain 14.2% chlorine.

To 600 grams of the above benzene solution there were slowly added (with thorough stirring) 50 grams of anhydrous ammonia dissolved in 300 grams of 98% isopropyl alcohol. Since this reaction takes place with great evolution of heat,

cooling or pressure is advisable to prevent loss of reaction for the preparation of the chlorinated product goes with great ease, even though the o'riginad phenolic compound may contain a long chain aliphatic substituent group.

Below are given numerous examples of the preparation of the new compositions of the present invention. The tertiary octyl phenol used in these examples was prepared by alkylation of phenol with diisobutylene. This alkylated phenol has also often been referred to as diisobutyl.

phenol, isooctyl phenol or tetramethylbutyl phenol.

Example 1 900 grams of paraformaldehyde (30 mole of formaldehyde) and 5000 grams of concentrated of 20 to 25 minutes, while passing dry hydrogen chloride gas continuously through the solution during the entire reaction in order to keep the mixture saturated with hydrogen chloride. The stirrerwas also operated continuously to provide efiicient contact between the two'liquid phases during the reaction. The temperature of the initial mixture of paraformaldehyde and hydrogen chloride was 15 C. It increased to 45-50" C. upon addition of the phenol and this temperature was thereafter maintained for 1 hours while constantly stirring and passing in hydrogen chloride gas. At the end of this time, after the the stirring was stopped, an upper phenolic benzene solvent and ammonia, especially in large scale preparations. After complete addition of the ammonia, the mixture consisted of a thick, tacky, yellow slurry containing an excess (about 10%) ofammonia. The mixture was then placed in a stainless steel bomb of one liter capacity, which was sealed and then heated for 20 hours at a temperature of to C.

After heatin the reaction product was obtained as a material completely soluble in' the benzene-alcohol solvent present which also contained a fine suspension of insoluble ammonium chloride. This mixture was washed with water several times to remove both the alcohol and the suspended salt. 500 grams of a refined paraffinic lubricating oil, having a viscosity Saybolt at 210 F. of 43 seconds, were added and the mixture was blown with nitrogenat 120 to C. for two hours to remove the benzene. After this,

more oil was added to provide a concentrate of For example, when conducting the. process as described in Example 1 with several different pro-i portions of formaldehyde and tert.-octyl phenol, the chlorine content of the intermediate product and the nitrogen content of the final product were observed to be as follows:

. Inter- Final Molnl ratio of formaldehyde to octyi mediate r du t phenol product 0 N per cent G] W Instead of removing the suspended ammonium chloride from the heat treated reaction product by water washing as described in Example 1, the salt may be'removed by filtration, preferably by filter pressing the suspension with the addition of a filter aid such as Hyfio. A suitable lubricating oil may then be added to the filtrate (if it is and further condensation or polymerization of grammatically by the present in the halide, an alcohol, ketone or olefin. by known alkylating methods, and with subsequent reduction by hydrogem'if needed or desired. .7 Asin exact mechanism of the reactionis not entirely understood. In the first stage the alkyl phenol may be regardedas condensing with the reaction product of the hydrogen halide and aldehyde, or as condensing with formaldehyde, the

product, it is to be understood that agents or similar character. How- .5 other similar reactants may be used.

product, e. g., with an i alkylating agent such as diethyl sulfate, an alkyl the case or many resin preparations. the

con-

densation product thereof being condensed with the hydrogen halide. The resulting product of this reaction is a complex mixture of various chlormethyl derivatives having the following general formula: V

in'iwhich the substituent groups may be attached to any position of the aryl nucleus indicated diahexagon, R representing a a hydrocarbon group of at least 2, and preferably an alkyl group of 4 or more, carbon atoms. and X representing hydrogen or an organic radical.

especially an alkyl, ,aryl or aralkyl radical-whichmay in turn contain which have been identified as 1 products from such reaction are substituent groups. Among the compounds the following:

ohlormethyl tem-octyl phenol I OH C 310 CHaCl 8H1! di(eblormethyl) tert.-octyl phenol j on on a a Quin-0150! 8H" 1H" chiormethyl bis (tert.-octyl hydroxy phenyl) methane an bis(tert.-octyl chlormethyl hydroxy phcnyl) methane ene (CH2--) grou radicals in the molecule, as, for

containing the following characteristic group:

wherein, before. R-Ar(OI-I)-- represents the allryl phenol group. X represents H or an organic hydroxy alkyl benzyl radical, andwhich may represent similar or diilerent example, in the following types of compounds:

' In a further variation of the method for producing the amino compounds used in accordance with this invention the hydrogen chloride and formaldehyde may first be reacted to form chlormethyl ethers such as C1CH2(OCH2) nOCHiCl, in which n is an integer, and these chlorethers may be caused to react be done by passin dry hydrogen chloride through -a suspension'ot paraformaldehyde in a solvent such as benzene until most of the formaldehyde has reacted with the hydrogen chloride to-give a soluble reaction hydroxy benzyl chloride or condensation products r of the same, the reagents being used preferably v in a ratio of about 2.5 mol equivalents of formaldehyde per mol of'phenol. This intermediate is reacted with ammonia and heated as in an oil-soluble product. The may also be prepared by any other suitable method and the mixed ether products may be fractionated to separate pure ethers, any one of which may be reacted with the phenol.

The phenol may also be added to the formaldehyde-benzene mixture and dry hydrogen chloride passed through this mixture to obtain the desired product in a single stage reaction.

' is reacted with ammonia and heated as before to give the lubricating oil additive, The reaction of hydrogen chloride and formaldehyde may also be conducted in the presence of may then be reacted ,with the alkyl phenol by without a catalyst, such as zinc a by-product.

Also, the alkyl phenol may be converted to the sodium salt and this salt, with no excess of alkali present, may then be caused to react with an aidehyde to give an alkylol derivative. This may be converted to the chloride by reaction with hydrogen chloride. Either the alkylol derivative or a thereby forming compounds CICHzOCHzCl and This product i and is conducted in in Example 1. When evaporated to recover resulting halide derivative may then be reacted in the following example.

Example 2 One molecular proportion each of tert.-octyl phenol (tetramethylbutyl phenol) and of sodium hydroxide are dissolved in water containing sufiicient alcohol to dissolve the resulting sodium phenolate. The and volume of methyl alcohol per volume of phenol is sui'hcient for this purpose. Three molecular proportions of formaldehyde (in the form of formalin containing 37% 01120) are added to this solution and the mixture allowed to stand for about 48 hours at room temperature, the reaction leading to the formation of the dimethyloi derivative. The reaction mixture is then neutralized with acetic acid or any suitable mineral acid and the liberated dhhydroxymethyl) tert.- octyl phenol separates be used directly as such or afterpuriflcation. To form the dichloride, the dithydroxymethyl) tert.- octyl phenol may be contacted with concentrated aqueous hydrochloric acid, or with dry hydrogen chloride. In the latter instance the hydrogen chloride may be passed through a solution of the compound in a suitable solvent such as benzene, carbon tetrachloride, chloroform, etc.

The reaction with ammonia may be carried out by adding an excess of ammonia, dissolved in isopropyl alcohoL to a solution of the hydroxy methyl tert.-octyl phenol orof the corresponding chloride in a solvent such as benzene. This reaction with ammonia is quite violent at first the addition of ammonia is completed, the reaction mixture is sealed in a bomb and heated at 110 to 120 C. for about 18 to 24 hours. The mixture is subsequently washed with water to remove isopropyl alcohol an am.- monium chloride and the benzene solvent is then the complex reaction prodduct as a brittle solid resin which is soluble in lubricating oils. Because of .its resinous nature, the rate of solution of the product in oil may be slow, particularly in base stocks of 'high viscosity index. To facilitate solution in such oils it is advisable to heat them to above 60-70 C. when preparing blends of the addition agent. This procedure may also be used to prepare concentrates containing as much as 25 to of the material, the concentrates later being mixed with additional base stock to give finished blends of the desired concentration.

It is possible to conduct the reaction of the phenol, formaldehyde and ammonia directly in a single stage by placing a mixture of suitable proportions of these reagents in a bomb and heating it, for example, at 110 to 140 C. for about 15 to hours. The proportions of reagents are preferabl similar to those used in the process described above, at least a moi equivalent of formaldehyde'and ammonia being used per moi of phenol. The ammonia is preferably in excess, some remaining at the end of the reaction. This is illustrated in the following example.

Example 3 and the bomb was quickly sealed. The bomb was as an upper layer and may the same manner as described Then 20 gramsuse of about 2 volumes of water a soft light colored resin, which upon analysis was I product was extracted with ether, and the ether extract was washed free of ammonia and subsequently dried over sodium sulfate. After the ether was removed by evaporation, there remained 50.5 grams of a. soft red resin which contained 1.3% nitrogen.

Another example, showing a somewhat varied procedure is as follows:

Example 4 A stainless steel bomb was charged with 150 cc. of absolute ethyl alcohol and 7.5 grams of trioxymethyiene. The solution was then saturated with ammonia gas at 0 C., the trioxymethyien'ebeing dissolved during the process of saturation. 17.5 grams of ammonia were absorbed, 55.5 grams of tert.-octyl phenol were then added, and the'.bomb was quickly closed and heated at C. for 20 hours. The bomb was then cooled, opened, and 'the reaction mixture poured into water and extracted with ether. The ether extract was washed free of ammonia with water and then dried over sodium sulfate. Evaporation of the ether yielded 62 grams of a found to contain 2.52% nitrogen. Upon heating this material at.20 C. for one-half hour under 3 mm. absolute pressure and then cooling, a brittle resin was obtained which had a nitrogen content of 0.56%. A portion of this material was then blended in 0.1% concentration with a turbine oil which normally caused heavy corrosion in a turbine oil corrosion test. The blend showed only very slight corrosionin this test and in fact this additive was found to be substantially as effective as the best anti-corrodants known.

As a variation of these processes, hexamethylenetetramine may be used in place of a mixture of formaldehyde and ammonia, and may be reacted by heating with the phenol, with or without a solvent.

Primary and secondary amines and substituted amines, such as diethyl amines, diamyl amines, piperidine, aniline, diphenyl amine, and substituted amines, such as ethanolamine and the like, may be substituted for the ammonia in any of the above described processes to prepare similar condensation products. These upon heating also undergo condensation and polymerization.

Similarly, more complex derivatives of hydroxy benzyl chloride may be prepared by any suitable methods and may be reacted with ammonia or a 1 primary or secondary amine and heated to secure resinous "condensation and polymerization products suitable for use in preparing the salts of the present invention. Examples of such hydroxy benzyl chlorides are on on OCHQCILOI on on CHLCQCHOCHMI and preferred that the phenols contain an "of at least 2, and preferably 4 or more, carbon atoms attached to the nucleus.

as those having may also be heated to produce resinous autocondensation products suitable for use in forming the salts of this invention. In the above formulas the substituents may be linked to any position of the .aryl nucleus, and the radicals R and R have the same significance as in the formulas previously described. This is illustrated by the following example:

Example 5 bath for 24 hours. The product was distilled under 3 mm. mercury absolute pressure, yielding a clear liquid distillate fraction at 163 to 165 C. and a residue which was a yellow, transparent, hard resin. This resin was found'to be active as an anti-corrodant in a turbine oil corrosion test,

although it was not quite as effective as the.

products of Examples 3 and 4.

Then phenols used in any of the above described processes include generally all nuclearly hydroxylated aromatic compounds having phenolic properties and a readily replaceable nuclear hydrogen atom which is preferably either ortho or para to the hydroxyl group. Phenols extracted from petroleum oilsmay also be used as obtained orafter' alkylation. Also, other naturally occurring phenols may be used, such as those having a vegetable origin, for example, cardanol, obtained from cashew nut shells. -As indicated above ,it is alkyl group complished by alkylating any of the abovedescrlbed phenols which do not already contain, suitable alkyl groups. The alkyl phenols may be prepared by alkylation of phenols with oleflns, including'mixtures of oleflns such as those ob- This may be actained in cracked petroleum fractions, and by 1 alkylation of phenols with alkyl halides, including chlorinated paraffin wax and chlorinated petrolatums derived from petroleum. Such chlorinated waxes may contain dichlorides and polychlorides and may be used in alkylating phenols by the customary Friedel-Crafts type of synthesis to give complex alkylated phenols of high molecular weight in which several phenol groups are linked by alkyl radicals in a single molecule. These high molecular weight complex alkyl phenolic products, when reacted with an aldehyde and a nitrogen base as described herein, give products which are effective in reducing the pour point of waxy oils and in raising the i viscosity index of lubricating oils as well as in improving their lubricating properties, such as film strength, and their stability and resistance to oxidation. i

In additionto the phenols, other hydroxy aromatic compounds may be employed in forming the hydroxyarylalkyl amines. For example, 'alfkyl'ated phenol sulfides or disulfldes may be employed. These may be reacted with formaldeof the latter in autccondensation.

OH OH 0H on elem-Q 0H,o

in which R is preferably an alkyl radical. The products may be reacted with ammonia or amines and resinifled in accordance. with the present invention.

Other hydroxy aromatic compounds may also be used in asimil'ar mannensuch as naphthols, hydroxy biphe'nyl, thymol, etc.

The foregoing description has related to methods of preparing the resinous autocondensation products of hydroxyarylalkyl amines. The metallic salts of-these products may be readily prepared byreacting the products with metallic bases, alcoholates, etc. For example, the octyl phenol-formaldehyde-hydrogen chloride-ammonia product of Example 1 may be reacted with barium hydroxide by heating with a dispersion mineraloii or benzene to form a barium salt in which the metal replaces hydrogen of a hydroxy group. The same'material may be reacted with an alcoholate, such as magnesium methylate or ethylate; or it may be reacted with an alkali, and the alkali salt so formed may be converted into other metallic salts by double decomposition, as in reacting with a salt of another metal. chlorides of polyvalent metals, such as magnesium, zinc and the like, work satisfactorily in the double decomposition, which is preferably conducted in absolute alcohol as the reaction medium. In preparing barium salts by this method, bariumbromide will I be found to be a more satisfactory reagent than the chloride because of its better solubility in alcohol. In general, about 5 to 10% excess, metal hydroxide overthe amount theoretically required will be suillcient for conversion of the condensa: tion products to their metal salts, but greater excesses than this may be necessary depending on reaction conditions and the particular products being handled.

Although in the preferredmethod of the present invention autocondensation of the hydroxyarylalkyl amines is first effected before conversion to the .metal salts, it may be found desirable in some instances to form the metal salt of the hydroxyarylalkyl amine before bringing about The onium salts of the resinous products of hydroxyarylalkyl amines may be prepared by reacting a halide of an onium base, e. g., a tetraalkyl ammonium chloride, a sulfonium chloride, or the like, with an alkali'metal salt of the resinous hydroxyarylalkyl amine, preferably in an alcoholic'solution. The alkali halide formed in the reaction is insoluble and may be conveniently removed.

The preparation of the salts from the compounds containing free hydroxy groups is illustrated by the following example of the preparation of a barium salt:

Example 6 145 grams of the ammonia derivative of chicromethyl tert.-octyl phenol, prepared, for example, by the method shown in Example 1, and 145 grams of C. P. benzene were refluxed with 215 grams of Ba(OH)z.8H2O for 60 hours, water being removed from the reaction through a trap in the reflux condenser. The mixture was filtered to give an approximately 50% solution of the barium salt in benzene. Analysis showed the product, on a benzene-free basis,' to contain 11.13% of barium. A product containing 10.87% barium on a solvent-free basis may, however, be obtained by refluxing the mixture for only 8 hours. The product on complete removal of the solvent was a brown powdery mass.

The invention thus contemplates the preparation of salts of high molecular weight resinous autocondensation products of hydroxyarylalkyl amines containing the characteristic structuret l-( i) in which R is an alkyl linkage such as in which R represents either H or alkyl or aryl groups or substituted alkyl or aryl groups and.

may represent similar or different groups in the same molecule, n represents a small whole number and X represents hydrogen or one or more organic radicals attached to the aryl nucleus, especially an alkyl, aryl or aralkyl radical which may in turn contain substituent groups, such as a hydroxy alkyl benzyl radical. The desired compounds are also characterized by having at least four carbon atoms in alkyl groups joined to'the aryl nucleus and/or to the amine radical (N=) and are further characterized in having undergone an autocondensation reaction to produce a resinous, viscous liquid to solid product of high molecular weight which is soluble in hydrocarbon oils. In this, as in all the other structural formulae given in this application, the location of the substituent radicals in regard to the aryl nucleus is given merely as an illustration, and the various substituent radicals may be attached to any positions of the aryl nucleus, ortho,

meta and/or para to the hyroxyl group and to each other. The most useful compounds of this invention come within the above definition and are salts of resinous autocondensation products or materials having the characteristic structure in which R is an alkyl group of at least 4 and preferably 5 to 20 or more .carbon atoms, the compounds having undergone an autocondensation reaction as described'above. Although the alkali and alkaline earth metal salts of the resinous autocondensation products of these compounds are especially useful, other divalent metal salts, such as the salts of zinc, copper and lead, should be particularly mentioned. The barium salts are exceptionally effective as lubricating oil additives. In place of the metallic salts the CO3- um and pyridonium salts, may also be used to I advantage.

A detailed procedure for conducting a small scale commercial preparation of a typical new composition of the present invention will be described in the example which follows. In this example paraformaldehyde is reacted with hydrogen chloride, the product is reacted with tert.- octyl phenol and the product thereby formed is further reacted with ammonia, and the amino compound thus produced is finally converted into the barium salt.

Example 7 fraction in order to observe the rate of flow, and

thus to a fume hood, maintaining the reactor at atmospheric pressure. After the air is expelled, the gas is passed in slightly faster than it can be absorbed in order to hydrohalogenate as rapidly as possible, maintaining the temperature at about 20 to 30 C. by circulating water through the jacket. After one hour the gas flow is stopped. 2060 grams (10 mols) of tert.-octyl phenol which have been melted by means of a steam coil are added to the'same reactor, or to another reaction vessel to which the entire product has been transferred, through a dropping fun nel or other suitable means, as rapidly as possible, holding the temperature in thereactionbelow 50 C. The flow of hydrogen chloride gas is resumed immediately at a rate just slightly faster than it is absorbed, maintaining atmospheric pressure and a temperature of approximately 50 C., for 2 'hours.

The introduction of hydrogen chloride is then discontinued and the mixture allowed to stand several hours, and dry ammonia gas is introduced under pressure through the tube extending to the bottom of the same reactor or of another reactor containing the product of the preceding reaction, and stirring is continued. When the ammonia is initially introduced, the outlet valve of the reactor is opened slightly so that any air present will be swept out by the incoming ammonia. During this step the gas pressure in the reactor is maintained at about 20 lbs/sq. in. When an atmosphere of substantially pure ammonia has been obtained, the outlet valve is closed and the pressure allowed to rise to from 25 to 50 lbs., where it is maintainedfor about 18 hours. The temperature is held at a maximum of C. by circulating water, then steam, through the jacket.

After ammonation is complete, the ammonia pressure is slowly released until atmospheric pressure is reached. and the product is removed from the reactor. The solid ammonium chloride which has formed is removed by filtration and the benzene solution is washed rapidly with water until the washings are substantially free 'of chlorides.

is to be used as such in a lubricating oil or conlayer may be separated from the mineral oil concentrate addition of of stearylor cetyl alcohol will greately miniaiimae tion, and the benzene and any residual water may then be removed under vacuum. In this manner, oil solutions containing to 75% of the product, may be obtained, although for convenience in handling, concentrates having to of additive are most often preferred.

If in the preparation of the chlormethyl phenol an aqueous layer is formed, the latter may be discarded. If emulsiflcation occurs, the emulsion benzene 'layer and the emulsion broken by treatment with live steam until the benzene begins to boil. on standing for an hour or more, a. separation of the aqueous and benzene layers will occur. The separated benzene layer may then be returned to the reactor.

The conversion of the product to ametal salt may be carried out in theabove benzene solution, or, more preferably, in a mineral oil solution. Thus, to prepare the barium salt 4000 grams of a 50% mineral oil solution 01 the condensation product obtained as described above are placed in a suitable reaction vessel and heated to C. Then 1600 grams of BB.(OH)2.8H2O are added gradually with stirring over a 1 to 2 hour period and heating continued for about 30 minutes, after-which the product is filtered to give a finished lubricating oil concentrate of'the metal salt.

To minimize foaming during the neutralization it is desirable to have present a foam suppressor such as a higher aliphatic alcohol. In a 50% about 3 to mize foaming and will also facilitat the subsequent filtering operation.

the purpose of illustraterms of the appended preparing a metallic phenolof an oil-soluble hydroxyarylalkyl amine product which comprises reacting 2 to 3 molecular proportions of formaldehyde with 1 molecular proportion of tert.-octyl phenol in the presence of hvdrogen chloride in proportions to form a product containing 10 to 15% of chlorine, reacting the latter with a sumcient quantity of ammonia to replace each atom of chlorine with an amino group, resinitying the product by means of auto-condensation, and further reacting the resinified product with a metallic base.

2. The process of preparing a metallic phenolate salt of an oil-soluble hydroxyarylalkyl'amine product which comprises reacting two to three molecularproportions of formaldehyde with one molecular proportion of an allwl phenol having an alkyl group of 4"to 20 carbon atoms and at leastgnehnsubstituted nuclear hydrogen atom in the presence of hydrogen chloride in proporproduct by means of autocondensation, and-further reacting the resinifled product-with a metallic base.

3. A process accordingto claim 2 in which the metallic base is barium hydroxide.

CHARLES n FLEMING, Js. JOHN-G. McNAJB.

particular examples, which have I 

